Radiation curable coating composition

ABSTRACT

Release coatings are provided by including in a liquid monomer or prepolymer polymerizable by electromagnetic or ionizing radiation a waxy material of limited compatibility therein. Upon application of a film of such material by casting, coating or printing, a thin layer of the waxy material migrates to the surface to provide, after cure, the desired release properties. The thin surface layer of waxy material also tends to exclude oxygen from the film to permit radiant curing in air. Preferably the polymerizable liquid comprises acrylate monomers with or without unsaturated prepolymers co-polymerizable therewith dissolved therein. Novel prepolymers especially useful for providing release films and other radiation curable coatings are described, including the reaction product of polyamides, containing primary and secondary amine groups with unsaturated polybasic carboxylic acids and particular reaction products of polyether triols with toluene diisocyanate, modified with unsaturated monomers. Also described is the inclusion in the polymerizable liquid of a dispersed substantially linear polymer as shrink control and re-inforcing agent.

CROSS-REFERENCE TO RELATED APPLICATION

This is a divisional of U.S. Ser. No. 575,252 filed May 7, 1975 for"RADIATION CURABLE COATINGS", which is in turn a continuation in part ofSer. No. 400,364 filed Sept. 24, 1973, now U.S. Pat. No. 3,989,609,issued Nov. 2, 1976.

BACKGROUND OF THE INVENTION

This invention relates to radiation curable and radiation cured coatingssuch as cast films, inks, varnishes and release coatings, methods ofmaking the same, and prepolymer materials suitable for making suchcoatings. These coatings are curable by ultraviolet radiation as well asby plasma arc and an electron beam radiation, which for the presentpurposes shall be deemed to be a form of radiation curing.

Coatings and inks for paper, foil, film, panels, tiles and the like aredesired which can be readily applied and which, after application, aretough, flexible, solvent resistant and abrasion resistant. Eliminationof solvents to reduce cost, to avoid pollution, and to achieve improvedproperties is desirable. Release surfaces of low adhesion are useful fortransfer printing, for temporary protective cover sheets forpressure-sensitive adhesives, and to facilitate handling of multiplearticles in machinery or the like.

Known radiation curable coatings useful for other purposes have beendeficient in one or more of the above described criteria. Either theyhave required long exposures to radiation, especially ultraviolet light,or they have limited strength, abrasion and solvent resistance. Suitablerelease coatings heretofore known have required use of materials such aswaxes or resins which inherently have release properties and have beenapplied as hot-melts or solvent solutions.

OBJECTS OF THE INVENTION

It is one object of the present invention to provide release surfaceswhich can employ a wide variety of film-forming materials and which canbe readily applied without substantial solvent and quickly cured byradiation, generally in one second or less under moderate exposure.

It is a further object of the present invention to provide novelradiation curable materials, and coatings resulting therefrom, whichcure rapidly under moderate exposure to give films with a desirablecombination of toughness, flexibility and resistance to solvents and toabrasion. Such films are useful as inks, release coatings, protectivevarnishes or the like.

DESCRIPTION OF THE INVENTION

As more fully described hereinafter, a valuable new class of releasematerials is provided by including oily or waxy materials in a radiationcurable, film-forming liquid in which these materials have limitedcompatability such that a thin layer thereof will migrate to the surfaceof a thin film of the liquid prior to cure. The materials have good slipor release properties, are generally lipophilic, and can comprise waxes,silanes, siloxanes, silicones, fluorocarbons, and the like. Whilegenerally non-reactive in the polymerizable liquid, they can containreactive groups. For example, stearyl acrylate can be used with acrylatemonomers and will migrate to the surface and orient with the stearylgroups toward the surface prior to reaction, and the acrylate groupswill coreact with the cross-linking acrylates. The quantity of oily orwaxy materials is not critical, provided enough is used to be effective,generally between about 0.1 and 10% by weight of the film-formingliquid. Undue excess should be avoided to avoid property degradation inthe film. About 0.5 to 4.0% by weight is usually most preferred.

The use of waxes in radiation curable liquids has been considered in theprior art to form an oxygen barrier at the surface to facilitate curingin air, but, as stated, for example in U.S. Pat. No. 3,864,133, theresult is unsatisfactory. However, we have found that some oily or waxymaterials when added in small amounts will considerably shorten thenecessary exposure time to actinic radiation for cure, e.g. stearylacrylate, cyclodedecane, low molecular weight vinylidene chlorideacrylonitrile copolymers, etc. Also, so far as is known, it has notheretofore been appreciated that such materials can advantageously beused to form dry-stripping (non-melting) release layers in separablelaminates of pressure-sensitive adhesives, transfer designs, or thelike. Furthermore, the addition of some of these oily or waxy materialswill lead to cured coatings with excellent vapor barrier properties(e.g. oxygen, water, etc.). Such coatings are desirable, for instance,on plastic bottles, tubs, containers in general for food. Some of themost desirable additives for this purpose are low molecular weightvinylidene chloride acrylonitrile copolymers, fluorocarbon oil or waxes,cyclododecane.

The oily or waxy materials above described can be incorporated in anysuitable radiation curable liquid including addition polymerizablemonomers and prepolymers having ethylenic unsaturation, such as acrylatemonomers and polyurethane/acrylate prepolymers, polyamides with aplurality of reactive amine groups reacted with ethylenicallyunsaturated polybasic carboxylic acids, acrylated epoxides and epoxideresins, also radiation curable systems consisting of unsaturated groupsand thiol groups (e.g. U.S. Pat. No. 3,950,569) catalyticallypolymerized with catalysts all as more fully described hereinafter andin the Examples.

Preferred radiation curable liquids for use in this invention comprisean unsaturated prepolymer mixed with acrylic monomers and additives asfurther described below. Suitable unsaturated prepolymers areunsaturated polyether-polyurethane prepolymers prepared by reactingpolyether polyols with bis-or polyisocyanates, including aromatic andaliphatic, and an unsaturated reagent or by reacting reactive polyamideswith dicarboxyalkenes, their anhydrides or their esters. In thepreparation of these prepolymers a step of driving off volatilematerials such as solvents can be avoided if an acrylic monomer is usedas the solvent (i.e. a monomer which normally would be admixed in thesucceeding formulation step). Sometimes an agent for inhibiting furtherpolymerization (depending upon the nature of the prepolymer) is present.

The prepolymers, which in some cases already contain an acrylic esterreagent, if an acrylic monomer is used as a solvent and/or if an excessof acrylic hydroxyalkyl ester was used in the prepolymer preparation,are then compounded on a mill with a further quantity of unsaturatedreagent, in this case one or more acrylic or methacrylic esters (whetheror not the same unsaturated reagent was used in preparing theprepolymer). Additives, as further described below, are approximatelyadded at this formulating stage. After milling the material is spread asa film and then irradiated briefly to cure it.

The preferred modified polyester polyurethane comprises reacting oneisocyanato group of toluene diisocyanate (TDI) with a polyether triol,three mols TDI per mol of triol, and then reacting at least a part andpreferably all of the other remaining isocyanato groups with anethylenically unsaturated, reactive hydrogen containing compoundcopolymerizable with the acrylate monomers. TDI is a particularlysuitable aromatic and isophoronediisocyanate is a particularly desirablealiphatic because their two isocyanato groups have differentreactivities, facilitating this stepwise condensation. Polyethers basedon polypropylene oxide are the preferred triols and trimethylol propanecondensed with propylene oxide with a molecular weight between about300-4500, preferably 700-1500, is most preferred. Hydroxyllower alkylacrylate or methacrylate are the preferred active hydrogen containingunsaturated compounds. It is further preferred that essentially allisocyanato groups remaining after condensation with triol be so reacted.It has been discovered that such prepolymers polymerize readily andrapidly under radiation to form inks and coatings with an excellentcombination of properties. Such preferred prepolymers are shown in theExamples, particularly Examples 1-9 and comprise condensation of 1 molof triol with 3 mols TDI and substantially 3 mols of hydroxy-lower alkylacrylate (or methacrylate).

It has been found that prepolymer materials of this invention cureextremely well with ultraviolet light and with electron beams. The filmsof the order of one mil or less cure readily with ultraviolet light.Thick films may require more penetrating radiation, particularly if apigment is present, and for these plasma arc radiation, electron beamradiation, or X-rays are desirable.

The preparation of unsaturated polyether-polyurethane prepolymers formaking radiation curable coatings in accordance with the inventionbegins with reacting a diisocyanate with a polyol at a temperature notexceeding 75° C. in the presence of a catalyst chosen for a low degreeof promotion of side reactions. Stannous octoate is preferred as acatalyst. Stannous butyrate and stannous laurate have also been foundusable. Because of the high viscosity of the reaction product, thereaction is carried out in a solvent. The solvent may be either ahydrocarbon such as toluene, in which case it must be removed byevaporation later, or it may be an acrylate material of the class ofmaterials suitable for use in ink and coating formulations, in whichcase the solvent may be allowed to remain in the product. Examples ofthe latter type of acrylate monomer solvents are: trimethylolpropanetriacrylate, 1,6-hexanediol-diacrylate, 1,3-butanediol diacrylate,neopentylglycol diacrylate, pentaerythritol tetramethacrylate, etc. Thesolvent must be dry to avoid the production of by-products.

The reaction in the solvent is carried out in a vessel equipped with anagitator and blanketed with nitrogen or dry air. The mixture is stirredat room temperature as the polyol is added to the diisocyanate and theaddition is carried out at such a rate that with the available watercooling the temperature of the reaction mixture does not rise above 50°C. Then, after an hour or so of maintaining the reaction mixture at 50°C. or just below that temperature, when approximately one half of theavailable isocyanate groups have been used up (as determined bytitration of aliquots), an unsaturated hydrocarbon bearing a hydroxylgroup, either an alcohol or a hydroxy ester, is added, preferablysomewhat in excess, as for example 10% in excess, of the amount neededto react with those isocyanate groups which are left unreacted after thereaction with the polyether polyol. At this point it is preferable toswitch from blanketing the reaction mixture with dry nitrogen toblanketing with dry air (oxygen is a good polymerization inhibitor).During this addition the reaction mixture may be permitted to rise to75° C., but no further. After the addition is terminated, thetemperature is raised to 90° C. and after an hour or so, when theisocyanate concentration has decreased to the desired level, e.g.0.1-0.2%, a small amount of p-methoxyphenol is added to inhibitpremature polymerization. When a hydrocarbon solvent is to be removed,it is best to remove the solvent under reduced pressure at a temperatureas low as possible, in order to avoid premature polymerization of theprepolymer. Another preferred unsaturated prepolymer is obtained byreacting ethylenically unsaturated di-or polyacids, their esters and/oranhydrides with low molecular weight polyamid-resins, containing primaryand secondary amine groups along the polymer chain as well as at theends thereof, (e.g. Emery resins by Emery Chemical Company and/orVessamid resins by General Mills Company). Depending on the desiredproperties of the cured coatings, these amine groups may be reactedpartly or completely with the unsaturated bis- or polyacids, esters oranhydrides. The more of the amine groups reacted, the tightercrosslinked and harder and more abrasion resistant the resultingcoatings will be.

As will be made clear from the following examples, the modifiedprepolymer material may be an oil, with or without an acrylate esteradmixture, or it may be a solid resin. The next step is to compound themodified prepolymer as above prepared with one or more acrylate monomersesters on a roller mill. It is preferred to have trimethylopropanetriacrylate included as one of the components of this material, and ofcourse sometimes this component is already there for having been used asa solvent in the previous step. Other acrylate monomer components foruse at this stage are acrylated epoxidized soybean oil, hydroxyethylacrylate, hydroxyethyl methacrylate, 1,4-butanediol diacrylate,neopentryl glycol diacrylate, pentaerythritol tetra-acrylate,pentaerythritol triacrylate, hexanediol diacrylate, tetraethyleneglycoldiacrylate, vinyl acrylate, N-vinyl pyrrolidone (V-pyrol by GAFCorporation), butyl acrylate, isodecylacrylate, octadecylacrylate,dimethyl aminoethyl methacrylate, acrylic acid, methacrylic acid,acrylamide and/or methylene bis-acrylamide, and the like. It ispreferred that the radiation curable liquid contain at least oneacrylate monomer which is trifunctional (ethylenically unsaturatedgroups) or higher to promote cross-linking in the cured film. Acrylicmonomers useful in this invention are meant to include acrylic ormethacrylic acids, preferably esters thereof, and preferably estersthereof condensed with polyols, polyamines and the like to formpolyacrylates, that is monomers having two or more, and preferably threeor more unsaturated acrylate groups.

It is also essential to introduce at this stage a small to moderateamount of a photoinitiator for coatings to be cured by UV or plasma arcradiation (i.e., by actinic light generally). Coatings to be cured byelectron beam or X-ray radiation do not require a photoinitiator. Thefollowing are suitable photoinitiators for coatings according to thisinvention: benzil, benzoin, benzoin alkyl ethers, acyloin derivatives ingeneral, benzophenone, acetophenone and Michler's ketone. Othercompounds useful as photoinitiators for this purpose are those listed inTable 5-13, page 132, Molecular Photochemistry by N. J. Turro (W.Benhamin, Inc., 1967). One such compound is "Sandoray-1000", which is ahomogeneous halogen containing alkylarylketone which has the appearanceof a white to yellow, free flowing powder that is also available inpaste form. This ketone has a bulk density of 550 grams per liter and amelting point between 153° and 158° F. It has a solubility in distilledwater of 0.0001 gram per liter and a solubility in acetone, toluene andethyl acetate of 500 grams per liter. Since acrylate monomers areessentially transparent to UV, sufficient photosensitizer should be usedto permit rapid polymerization under moderate irradiation, preferablyunder 1 second. From about 0.5 to about 20% by weight can be used withabout 5-10% by weight of coating solution being preferred.

Where a release coating or oxygen barrier is to be provided, there isintroduced at this stage between one tenth of 1% and a few percent ofwax, e.g., between about 0.1% and about 10% by weight, either paraffinwax, ester wax, a fluorocarbon wax or some other oily or waxy materialsuch as a higher alkyl alcohol or acid or oleamide, or asilicon-containing material such as polysiloxane, silicone or silane ora mixture of some of these. Most of these materials are only slightlysoluble in the acrylic coating formulation, and form an emulsion or afine suspension. On curing under actinic light apparently thesematerials are expelled by the increasing crosslink density of thenetwork and form a thin film on the surface of the coating. Even a smallquantity of such material tends to migrate to the surface of the coatingand provides a release type surface with characteristics similar tothose of fluorocarbon polymers or silicones.

When the monomers added at this stage are such as to produce a mixtureof low viscosity, the result is a coating material very useful as anoverprint varnish. The coating can be cured by an exposure toultraviolet radiation from a medium pressure mercury lamp for from 0.1second to several seconds to form a hard, glossy coating. When themonomers added are such as to produce a heavy oil, the resultingmaterial is useful for coating rigid panels, such as paperboard orveneer panels, with a film having a thickness of one to several mils. Inthis case ultraviolet light may be insufficient to provide quick curingand higher energy radiation can be used, such as electron beam radiationon X-rays. In the absence of air, an exposure to about 2-6 Mrad issufficient for curing with electron beam radiation. In the presence ofair, 10-20 Mrad or more are sometimes needed.

For the manufacture of inks having the desirable qualities of thecoatings of the invention, pigments such as Lithol rubine pigment,molybdate orange, chrome yellow, phthalocyanine blue, carbon black ordyes are mixed in at the same time as most of the acrylic monomers. Herealso it is necessary to add 5-20% of a photoinitiator to inks intendedto be curable by actinic radiation, e.g. UV or plasma arc radiation,etc. The resulting ink may be printed onto paper, paperboard, plasticfilm, metal or other stock, and the printing can be rapidly cured byexposure for a fraction of a second to ultraviolet light from a lowpressure mercury lamp. An abrasion resistant and solvent resistantprinting is thereby produced, which does not require an overprintvarnish.

As a further aspect of the present invention, it has been foundadvantageous to include in the radiation curable liquid solution anessentially linear polymer which is soluble therein, preferably onehaving a molecular weight of about 4,000 to the limit of solubility, andpreferably between about 10,000 and 20,000. Such addition has been foundto improve the physical properties of the cured films by reinforcementand to limit shrinkage. This is especially useful with acrylate monomerswhich may have relative high shrinkage on curing and which are highlycross-linked.

The foregoing aspects of the invention are illustrated in detail in thefollowing examples wherein all parts are by weight. Examples 1-9 and15-22 illustrate the preparation of prepolymers used in the formulationsdescribed in Examples 10-14 and 23-26. Examples 27-104 referparticularly to release type coatings. Examples 104-114 illustrate theadvantageous inclusion of linear polymers in the radiation curablecoatings. Examples 115 and 116 demonstrate the preparation of coatingswith excellent oxygen barrier properties based on a radiation curableacrylic system; Examples 117 and 118 are oxygen barrier coatings basedon a radiation curable epoxide system, while Examples 119 and 120 areoxygen barrier coatings based on a polyene-polythiol system.

EXAMPLE 1

522 parts 2,4-toluene diisocyanate, 500 parts dried toluene and 0.5parts stannous octoate are placed in a vessel equipped with an agitatorand blanketed with nitrogen. With stirring, a solution of 735 parts poly(propylene oxide) triol (Dow Voranol, CP 700, Hydroxyl No. 229; 0.02% H₂O) in 750 parts dried toluene is added at such a rate that thetemperature of the reaction mixture does not exceed 50° C. The reactionmixture is stirred at 50° C. for 1 hour. Then the nitrogen blanket isreplaced by a dry air blanket and 383 parts hydroxyethyl acrylate (10%excess), mixed with 100 parts of dried toluene, are added at such a ratethat the temperature of the mixture does not rise above 75° C. After theaddition is completed, the reaction mixture is kept stirring at 90° C.for 1 hour. 1 part p-methoxy phenol (polymerization inhibitor) is addedand the solvent is removed under reduced pressure at or below 30° C.1650 parts of a clear, colorless, resinous oil, containing a trace oftoluene solvent are obtained. Analysis of this material shows 0.06%isocyanate content.

EXAMPLE 2

522 parts 2,4-toluene diisocyanate, 500 parts dried toluene and 0.5 partstannous octoate are placed in a vessel equipped with an agitator andblanketed with nitrogen. With stirring, a solution of 735 parts poly(propylene oxide) triol (Dow Voranol CP700; Hydroxyl No. 229; 0.02% H₂O) in 750 parts dried toluene is added at such a rate that thetemperature of the reaction mixture does not exceed 50° C. The reactionmixture is stirred at 50° C. for 1 hour. Then 191.4 parts allyl alcohol(10% excess) are added at such a rate that the temperature of themixture does not rise above 85° C. After the addition is completed, thereaction mixture is kept stirring at 90° C. for 1 hour. 1 part p-methoxyphenol (polymerization inhibitor) is added and the solvent is removedunder reduced pressure at or below 30° C. 1440 parts of a clear,colorless, resinous oil, containing a trace of toluene, are obtained.Analysis of the resulting material shows 0.04% isocyanate content.

EXAMPLE 3

522 parts 2,4-toluene diisocyanate, 780 parts trimethylol propanetriacrylate, and 0.5 parts stannous actoate are placed in a vesselequipped with an agitator and blanketed with nitrogen. With stirring,735 parts of poly (propylene oxide) triol (Dow Voranol CP700; hydroxylNo. 229; 0.02% H₂ O) are added at such a rate that the temperature ofthe reaction mixture does not rise above 50° C. The reaction mixture iskept at this temperature for an additional 1 hour. Then the nitrogenblanket is replaced by a dry air blanket and 383 parts hydroxyethylacrylate (10% excess) are added at such a rate that the temperature ofthe reaction mixture does not exceed 75° C. The reaction mixture isstirred for an additional 1 hour at 90° C. Then 1 part p-methoxy phenolis added and the reaction mixture is allowed to cool to roomtemperature. The product, 1605 parts of unsaturated prepolymer in 780parts of trimethylolpropane triacrylate and 35 parts of hydroxyethylacrylate, is a clear, colorless, viscous oil. Analysis of the resultingmaterial shows 0.06% isocyanate content.

EXAMPLE 4

522 parts 2.4-toluene diisocyanate, 780 parts trimethylolpropanetriacrylate, and 0.5 part stannous octoate are placed in a vesselequipped with an agitator and blanketed with nitrogen. With stirring,735 parts of poly (propylene oxide) triol (Dow Voranol CP700; HydroxylNo. 229; 0.02% H₂ O) are added at such a rate that the temperature ofthe reaction mixture does not rise above 50° C. The reaction mixture iskept at this temperature for an additional 1 hour. Then 191.4 partsallyl alcohol (10% excess) are added at such a rate that the temperatureof the reaction mixture does not exceed 75° C. The reaction mixture isstirred for an additional 1 hour at 90° C. Then 1 part p-methoxy phenolis added and the reaction mixture is allowed to cool to roomtemperature. The product consists of 1413 parts unsaturated prepolymerin 780 parts trimethylolpropane triacrylate and 17.4 parts allylalcohol. It is a clear, colorless, viscous oil. Analysis of theresulting material shows 0.03% isocyanate content.

EXAMPLE 5

188.6 parts isophoronediisocyanate, 292.3 parts trimethylol propanetriacrylate, and 0.17 parts stannous octoate are placed in a vesselequipped with an agitator and blanketed with nitrogen. With stirring,200.7 parts of poly (propylene oxide) triol (Dow Voranol CP700; hydroxylNo. 229; 0.02% H₂ O) are added at such a rate that the temperature ofthe reaction mixture does not rise above 60° C. The reaction mixture iskept at this temperature for an additional 1 hour. Then the nitrogenblanket is replaced by a dry air blanket and 118.0 parts hydroxyethylacrylate (10% excess) are added at such a rate that the temperature ofthe reaction mixture does not exceed 75° C. The reaction mixture isstirred for an additional 1 hour at 80° C. Then 1 part p-methoxy phenolis added and the reaction mixture is allowed to cool to roomtemperature. The product, 1605 parts of unsaturated prepolymer in 780parts of trimethylolpropane triacrylate and 35 parts of hydroxyethylacrylate, is a clear, colorless, viscous oil. Analysis of the resultingmaterial shows 0.06% isocyanate content.

EXAMPLE 6

750 parts p,p'-diphenylmethane diisocyanate, 1000 parts toluene, and 0.5part stannous octoate are placed in a vessel equipped with an agitatorand blanketed with nitrogen. The mixture is stirred at room temperatureand 258 parts poly (propylene oxide) triol (Voranol CP260; Hydroxyl No.653; 0.02% H₂ O) are added at such a rate that the temperature of thereaction mixture does not rise above 50° C. The reaction mixture is keptat this temperature for an additional 1 hour. Then the nitrogen blanketis replaced by a dry air blanket and 383 parts of hydroxyethyl acrylate(10% excess) are added at such a rate that the temperature of thereaction mixture does not exceed 75° C. After the addition isterminated, the temperature of the reaction mixture is raised to 90° C.for 1 hour. After adding 1.0 parts p-methoxy phenol, the reactionmixture is allowed to cool to room temperature and the solvent isremoved under reduced pressure at or below 30° C. The product, 1398parts, is a clear off-white resin. Analysis of the resulting materialshows 0.01% isocyanate content.

EXAMPLE 7

1746 parts dimeryl diisocyanate, 500 parts dried toluene, and 1.0 partstannous octoate are placed in a vessel equipped with an agitator andblanketed with nitrogen. With stirring, 258 parts poly (propylene oxide)triol (Dow Voranol CP260; Hydroxyl No. 653; 0.02% H₂ O) are added atsuch a rate that the temperature of the reaction mixture remains below50° C. After the addition is completed, the reaction mixture is kept at60° C. for 2 hours with stirring. Then 191.4 parts of allyl alcohol (10%excess) are added at such a rate that the temperature of the reactionmixture does not exceed 75° C. After the addition is completed thetemperature is raised to 90° C. and the reaction mixture is keptstirring at this temperature for 2 hours. Then 1.0 part p-methoxy phenolis added, and the solvent is removed under reduced pressure. 2185 partsclear, colorless heavy oil is obtained as the product. Analysis of theresulting material shows 0.08% isocyanate content.

EXAMPLE 8

774 parts 4,4'-dicyclohexylmethane diisocyanate, 1000 partstrimethylolpropane triacrylate, and 0.5 part stannous oxtoate are placedin a vessel equipped with an agitator and blanketed with nitrogen. Themixture is stirred at room temperature and 735 parts of poly (propyleneoxide) triol (Dow Voranol CP700; Hydroxyl No. 229; 0.02% H₂ O) are addedat such a rate that the temperature does not exceed 50° C. After theaddition is completed, the reaction mixture is kept stirring at 50° C.for an additional 1 hour. Then the nitrogen blanket is replaced by a dryair blanket and 383 parts hydroxyethyl acrylate (10% excess) are addedat such a rate that the temperature of the reaction mixture does notrise above 75° C. Following this step the reaction mixture is stirredfor 2 hours at 90° C. Then 1.0 part p-methoxyphenol is added and thereaction mixture is allowed to cool to room temperature. The product, aclear, colorless, viscous oil, consists of a mixture of 1857 partsunsaturated prepolymer, 1000 parts trimethylolpropane triacrylate, and35 parts hydroxyethyl acrylate. Analysis of the resulting material shows0.06% isocyanate content.

EXAMPLE 9

348 parts 2,4-toluene diisocyanate, 500 parts dried toluene, and 0.5part stannous octoate are placed in a vessel equipped with an agitatorand blanketed with nitrogen. Then 407 parts poly (propylene oxide) diol(Dow Vornal P400; Hydroxyl No. 275; 0.02% H₂ O) are added at such a ratethat the temperature of the reaction mixture does not rise above 50° C.The reaction mixture is stirred at this temperature for an additionalhour. Following this step, 286 parts hydroxyethyl methacrylate (10%excess) are added at such a rate that the temperature of the reactionmixture is raised to 90° C. and the stirring continued for an additional1 hour. At the end of this period 1.0 part p-methoxy phenol is added andthe solvent is removed under reduced pressure. A clear, colorless,viscous oil is obtained as the product. Analysis of the resultingmaterial shows 0.02% isocyanate content.

EXAMPLE 10 UV Curable Overprint Varnish

100 parts of the product of Example 1, 235 parts trimethylolpropanetriacrylate, 30 parts hydroxyethyl acrylate, 3 parts stearyl acrylateand 25 parts benzoin isobutyl ether are mixed well on a roller mill. Aclear, colorless homogeneous light oil is obtained as the product.

Films of 0.4 mil thickness are applied with a wire wound coating rodonto paper, aluminum foil, vinyl coated aluminum foil, polyester coatedmylar, and steel. The coated substrated are exposed for 1/10 second tothe UV radiation given off by a medium pressure mercury vapor lamp(Hanovia 200 W/inch) at a distance of 5" from the lamp. This distancecoincides with the second focal point created by the ellipticalreflector.

After this exposure all samples are cured to hard, glossy coatings witha pencil hardness of at least 2H and a rub-resistance of at least 40rubs, using methyl ethyl ketone as the solvent.

EXAMPLE 11 UV Curable Overprint Varnish

20 parts reaction product from Example 3, 8 parts trimethylolpropanetriacrylate, 12 parts 1.4-butanediol diacrylate 10 parts acrylatedepoxidized soybean oil (Union Carbide Co. Actomer X-70), 10 partsacrylic acid, 0.4 part stearyl acrylate and 2.75 parts benzoin isobutylether are mixed on a roller mill. A homogeneous, clear, colorless lightoil is obtained. Films are applied and cured as shown in Example 10. Thecured films have a pencil hardness of HB, are insoluble in solvents andrub resistant.

EXAMPLE 12 Electron Beam Curable Coating

30 parts of reaction product from Example 3, 20 parts trimethylolpropanetriacrylate and 10 parts neopentyl glycol diacrylate are mixed on aroller mill. A clear, colorless heavy oil is obtained as the product.Steel and wood panels are coated with this composition with a 1 mil filmknife. The coated test panels are exposed to 6 Mrad electron beamradiation under exclusion of air. After the irradiation, the coatingsare clear, colorless, and glass-like. They have a pencil hardness of 4H,show excellent adhesion to metal and wood and are unaffected by solvent.

EXAMPLE 13 Electron Beam Curable Coating

20 parts reaction product from Example 3, 10 parts trimethylolpropanetriacrylate, 10 parts reaction product from Example 9, 10 partsacrylated epoxidized soybean oil (Union Carbide Co. Actomer X-70), 10parts neopentyl glycol diacrylate and 1 part stearyl acrylate are mixedon a roller mill until homogeneous. A clear, colorless, medium viscosityoil is obtained. Coatings of 4 mil thickness are applied with a filmknife to asphalt tile, vinyl asbestos tile, vinyl tile and wood. Thecoated panels are exposed to 6 Mrad electron beam radiation underexclusion of air. After the irradiation, the coatings are tough, clear,colorless and very abrasion resistant.

EXAMPLE 14 UV Curable Ink

60 parts of reaction product from Example 3, 10 parts Lithol rubinepigment, 10 parts pentaerythritol tetraacrylate and 3 parts stearylacrylate are mixed and ground on a three-roll mill until homogeneous.Then 5.4 parts benzoin isobutyl ether dissolved in 10 partstrimethylolpropane triacrylate are added and the milling is continueduntil the sensitizer is incorporated. The ink is applied to paper stockas a film of 0.1-0.4 mil thickness by means of a rubber roller. Completecure of the ink is achieved by exposure to UV radiation for 0.5 secondas described in Example 10.

Modified Polyamide Prepolymers

As previously mentioned, modified polyamide prepolymers prepared inaccordance with the invention are also radiation curable and likewiseuseful for overprint varnishes, for protective films on panels and tilesand for abrasion and solvent resistant inks.

A preferred starting material for the preparation of these modifiedprepolymers is a polyamide polyamine, a material that is made bycondensing an excess of polyamine with polycarboxylic acids, giving astill reactive condensation product. These are available in somevariety, for example, under the trade names of Versamid and Emerez. Ofcourse the modification in accordance with the invention could be madepart of the original polyamide process, just as was above described inconnection with the polyurethane process. It is convenient, however, touse these polyamide polyamine materials as starting materials. Thematerials are sometimes known as reactive polyamide resins and containprimary and secondary amine groups.

The above-described starting material is mixed with a smaller portion ofan ethyl or methyl ester, or an anhydride, or an unsaturateddicarboxylic acid. The reaction mixture is stirred at a temperature suchas 90° C. for a few hours and a slow stream of nitrogen is used to carryoff the methanol or ethanol, which may be recovered by a cold trap. Thereaction mixture is then stripped at low pressure (0.1 mm Hg), whilestirring at 90° C. to remove unreacted ester and more methanol orethanol. Finally, the product is allowed to cool in the presence of asmall amount of p-methoxyphenol to inhibit premature polymerization. Theester that is recovered during low pressure stripping may be anisomerization product of the ester supplied to the reaction. Thus,dimethyl maleate may be rearranged into dimethyl fumarate, and dimethylitaconate may be partly isomerized to the mesaconate and thecitraconate.

The products of the reaction described are in some cases oils and inother cases resins. They are thereafter compounded on a roller mill withacrylic monomer esters, additives and then films are prepared and curedfrom the resulting mixture in substantially the same manner as alreadydescribed in connection with the unsaturated polyether-polyurethanprepolymers. Further details regarding this aspect of the invention willbe apparent from the following illustrative examples.

EXAMPLE 15

205 parts of a reactive polyamide resin (derived from the condensationof polymerized fatty acids with polyalkylamines and containing primaryand secondary amine groups; General Mills Chemicals, Versamid 115, aminenumber 238) and 30 parts of dimethyl maleate are mixed in a vesselequipped with an agitator. The vessel is swept with a slow stream ofnitrogen while the reaction mixture is stirred at 90° C. for 3 hours.During this time 3 parts of methanol (identified by gas chromatography)are recovered from the off-gas by means of a cold trap. In order toremove any unreacted dimethyl maleate, the reaction mixture is strippedat 0.1 mm Hg pressure while stirring at 90° C. During this time another2 parts of methanol are recovered, but no unreacted dimethyl maleate.Then 0.1 part p-methoxyphenol is added and the product is allowed tocool to room temperature. 230.2 parts of a resinous, clear, but slightlyyellowish oil are obtained. It is calculated that the ratio (dimethylmaleate reaction)/(amine) is equal to 0.25.

EXAMPLE 16

This preparation is carried out as described in Example 15. 100 partsVersamid 115 are reacted with 40 parts dimethyl maleate for 3 hours at90° C. On stripping under reduced pressure approximately 17 parts ofdimethyl fumarate and approximately 4 parts of methanol are recovered(both components are identified by gas chromatography). After adding0.05 part p-methoxyphenol, the product is allowed to cool at roomtemperature. 117 parts of a greenish-yellow resin are obtained. It iscalculated that the ratio (dimethyl maleate reacted)/(amine is equal to0.35.

EXAMPLE 17

This preparation is carried out as described in Example 15. 99.1 partsVersamid 115 and 40 parts dimethyl maleate are reacted at 90° C. for 5hours. Approximately 6 parts methanol are formed during this time. Afteradding 0.05 part p-methoxyphenol, the reaction mixture is stripped underreduced pressure. Approximately 13 parts of dimethyl fumarate arerecovered. 124 parts of a greenish resin are obtained. It is calculatedthat the ratio (dimethyl maleate reacted)/(amine) is equal to 0.52.

EXAMPLE 18

100 parts reactive polyamide resin (General Mills Chemicals, Versamid100, amine number 90) and 30 parts diethyl maleate are reacted fro 5hours as described in Example 15. During this time 5 parts ethanol areformed. Then 0.05 part p-methoxyphenol is added. On stripping underreduced pressure an additional small amount of ethanol and 6 partsdiethyl fumarate are recovered. 116 parts product are obtained as aresidue. The product is a clear, yellowish resin. It is calculated thatthe ratio (diethyl maleate reacted)/(amine) is equal to 0.80.

EXAMPLE 19

100 parts reactive polyamide resin (Emery Industries, Emerez 1515; aminenumber 345) and 50 parts dimethyl maleate are reacted for 4 hours at 90°C. as described in Example 15. During this time 8 parts methanol arerecovered from the off-gas in a cold trap. On stripping under reducedpressure 5 parts unreacted dimethyl fumarate are recovered. Than 0.05part p-methoxyphenol is added and the product is taken as a residue. 135parts clear, yellow resin are obtained. It is calculated that the ratio(dimethyl maleate reacted)/(amine) is equal to 0.51.

EXAMPLE 20

100 parts reactive polyamide resin (General Mills Chemicals, Versamid115, amine number 238) and 30 parts 5-norbornene-2,3-dicarboxylicanhydride are mixed in a vessel equipped with an agitator and blanketedwith nitrogen. The reaction mixture is stirred at 90° C. for 3 hours.Then the reaction mixture is stripped at 90° C. under reduced pressure(0.1 mm Hg). No unreacted 5-norbornene-2,3-dicarboxylic anhydride isrecovered. 0.05 part p-methoxyphenol is added, and the product is takenas a residue. A glass-like, yellowish solid, soluble in tetrahydrofuran,methylene chloride, etc. is obtained. It is calculated that the ratio(5-norbornene-2,3-cicarboxylic acid reacted)/(amine) is equal to 0.43.

EXAMPLE 21

100 parts reactive polyamide resin (General Mills Chemicals, Versamid115, amine number 238) and 15 parts dimethyl maleate are reacted for 3hours as described in Example 15. After stripping at 90° C. and 0.1 mmHg pressure, 20 parts of 5-norbornene-2,3-dicarboxylic anhydride areadded. The reaction mixture is stirred at 90° C. under a nitrogenblanket for another 3 hours. Then 0.05 part p-methoxyphenol is added andthe reaction mixture is allowed to cool to room temperature. Anextremely viscous resin is obtained. It is calculated that 24.5% of theamine groups are reacted with dimethyl maleate and 28.7% with5-norbornene-2,3-dicarboxylic anhydride.

EXAMPLE 22

100 parts Versamid 115 are reacted with 45 parts dimethyl itaconate for3 hours at 90° C. as described in Example 15. Then the reaction mixtureis stripped at 0.1 mm Hg pressure. Approximately 3 parts of methanol and20 parts of a mixture of diemthyl mesaconate, dimethyl itaconate anddimethyl citraconate (identified by gas chromatography) are removed fromthe reaction mixture. 0.05 parts p-methoxyphenol is added and theproduct is taken as a residue. 120 parts clear, yellowish viscous oilare obtained.

EXAMPLE 23 UV Curable Overprint Varnish

100 parts of the product of Example 15, 135 parts trimethylolpropanetriacrylate, 30 parts hydroxyethyl acrylate, 2 parts paraffin wax (Essowax 3150; m.p. 135° C.), and 10 parts benzoin isobutyl ether are mixedwell on a roller mill. A clear, almost colorless, medium oil isobtained.

Films of 0.4 mil thickness are applied with a wire wound coating rodonto paper, aluminum foil, vinyl coated aluminum foil, polyester coatedmylar, and steel. The coated substrates are exposed for 1/10 second tothe UV radiation given off by a medium pressure mercury vapor lamp(Hanovia, 200 W/inch) at a distance of 5" from the lamp. This distancecoincides with the second focal point created by the ellipticalreflector.

After this exposure, all the coatings are cured. They have a pencilhardness of at least 3H and rub resistance of at least 40 rubs usingmethyl ethyl ketone as the solvent.

EXAMPLE 24 Electron Beam Curable Coating

20 parts of reaction product from Example 16, 20 partstrimethylolpropane triacrylate, and 20 parts neopentyl glycol diacrylateare mixed on a roller mill. A clear, slightly yellowish medium oil isobtained. Steel, wood aluminum and plastic panels are coated with thisformulation using a 1 mil film knife. The coated test panels are exposedto 6 Mrad electron beam radiation under exclusion of air. After theirradiation, the coatings are clear, colorless, hard and glasslike. Theyhave a pencil hardness of 4H, show excellent adhesion and are unaffectedby solvents.

The same type of coatings are cured in presence of air by exposing themto 20 Mrad electron beam radiation.

EXAMPLE 25 Electron Beam Curable Coating

20 parts product from Example 22, 10 parts trimethylolpropanetriacrylate, 10 parts 1,6-hexane-diol diacrylate, 10 parts acrylatedepoxidized soybean oil (Union Carbide Co., Actomer X-70), and 1 partstearyl acrylate are milled on a roller mill until homogeneous. A clear,almost colorless, medium viscosity oil is obtained. Coatings of 4 milthickness are applied with a film knife to asphalt tile, vinyl tile andwood. The coated substrates are exposed to 5 Mrad electron beamradiation under exclusion of air. After the exposure the coatings aretough, clear colorless, not affected by solvents, and are very abrasionresistant.

EXAMPLE 26 UV Curable Ink

50 parts of reaction product from Example 16, 20 partstrimethylolpropane triacrylate, 10 parts Lithol rubine pigment, and 3parts stearyl acrylate are mixed and ground on a three-roll mill untilhomogeneous. Then 5.5 parts benzoin isobutyl ether, dissolved in 10parts trimethylolpropane triacrylate are added and the milling iscontinued for a short time. The ink is applied to paper stock as a filmof 0.1-0.4 mil thickness by means of a rubber roller. Complete cure ofthe ink is achieved by exposure to UV radiation for 0.5 seconds asdescribed in Example 9.

The radiation curable coatings of this invention are extremely usefulfor making hard coatings without the application of extensive heat tothe coated surface, and without the necessity of depositing an alreadycured resin from a solvent which must then be evaporated and recovered.The modified prepolymers of the present invention make it possible toprepare hard coatings by spreading a prepolymer material of convenientfluidity and then quickly curing the film to make it resistant toabrasion and to solvents.

RELEASE COATINGS EXAMPLE 27

10 parts dimethyl maleate-modified reactive polyamide resin (versamid115--General Mills Chemicals--reacted with 40% by weight of dimethylmaleate at 90° C. for 3 hours, excess dimethyl maleate removed underreduced pressure) are mixed with 10 parts pentaerythritol tetraacrylate,0.01 part phenothiazine, 0.4 part Esso wax 3150 (paraffin wax, m.p.approx. 132° C.), 0.8 part benzoin isobutyl ether and 20 parts methylenechloride. A clear, low viscosity oil is obtained.

A carrier paper made of smooth clay coated sheet weighing about 16pounds per ream (500 sheets, 20×25 inches) is coated with the abovesolution using a #20 Mayer rod. The coated paper then is exposed for1/10 second to the UV radiation given off by a medium pressure mercuryvapor lamp (Hanovia, 200 W/inch) at a distance of 5 inches from thelamp. This distance coincides with the second focal point created by theelliptical reflector. By this exposure, the coating is cured to a hard,glossy film which has a pencil hardness of 3H.

The radiation cured release coating is then print coated with a clearlacquer composed of 6 parts cellulose acetate-buryrate (Eastman EAB171-40), 55 parts ethylacetate, 28 parts toluene, and 11 parts 95%ethanol (Printing grade). Print coating is accomplished using a regularvarnish etch cylinder having a depth of about 20 to 40 microns, 120 linescreen and a 15-20 wall (equivalent to #8 Mayer rod). The appliedlacquer coating is dried at 140° F. for 1 minute.

The design print is then printed over the clar lacquer layer usingpolyamide-nitrocellulose modified ink containing pigment or dye of thecolor desired (ZYROTO WHITE, sold by Gotham Ink and Color Co., whichcontains a titanium dioxide pigment). The area of the design print issmaller than that of the printed lacquer layer and falls wholly withinthe margin of the lacquer layer.

Over the ink, as an overprint, there is then coated a clear adhesivelayer comprising a solution of heat-activatable thermoplastic polyamideresin in lacquer form (VERSAMIDE 940, sold by General Mills) followed bydrying the adhesive to a dry non-tacky state. The area of the adhesiveoverprint is smaller than that of the lacquer and it falls wholly withinthe margins of the lacquer layer.

There is no pick-up during the three printing operations.

The heat transfer label, as formed above, is then put in contact with apolyethylene bottle, the surface of which has been treated to render itmore print receptive in a conventional manner such as by flame contact.Heat and pressure are applied to the temporary backing to effectpressing of the adhesive layer against the polyethylene surfaces. Asheat is applied, approximately 350° F., there is no softening of therelease layer or the cellulose acetate layer, but the adhesive overprintis heat-activated to a highly tacky state and bonds to the polyethylenesurface of the bottle. The temporary backing may then be stripped fromthe transfer label or may be left on the transfer and stripped at asubsequent time without danger of delaminating the transfer from thepolyethylene surface. No portion of the release layer is left over thetransfer after stripping of the temporary backing and no portion of thelacquer is removed with the release layer. After cooling and peeling ofthe temporary backing, the bottle so coated is flame treated and theadherence of the label thereto is determined. Adherence was excellent.

EXAMPLE 28

Same as Example 27, except that 1.0 part of cyclododecane is used inplace of the Esso Wax 3150.

EXAMPLE 29

Same as Example 27, except that 1.0 part stearic acid is used in placeof Esso Wax 3150.

EXAMPLE 30

Same as Example 27, except that 1.4 parts-methanacryl oxypropyltrimethoxy silane (Union Carbide silane A-174) are used in place of theEsso Wax 3150.

EXAMPLE 31

Same as Example 27, except that 0.6 part E-wax (Farbwerke Hoechst AB,Montan type wax) is used in place of the Esso Wax 3150.

EXAMPLE 32

Same as Example 27, except that 1.0 part FL-wax (Farbwerke Hoechst AB,Montan type wax) is used in place of the Esso wax 3150.

EXAMPLE 33

Same as Example 27, except that 1.4 parts F-wax (Farbwerke Hoechst AB,Montan type wax) are used in place of the Esso wax 3150.

EXAMPLE 34

Same as Example 27, except that 0.5 part octadecanol is used in place ofthe Esso wax 3150.

EXAMPLE 35

Same as Example 27, except that 1.0 part oleamide (Armour IndustrialChemical Co., Armid O) is used in place of the Esso wax 3150.

EXAMPLE 36

Same as Example 27, except that 1.4 parts stearyl acrylate are used inplace of the Esso wax 3150.

EXAMPLE 37

Same as Example 27, except that 0.6 part isodecyl acrylate is used inplace of the Esso wax 3150.

EXAMPLE 38

Same as Example 27, except that 1.0 part fluorolube LG-160 (HookerChemical Co.) is used in place of the Esso wax 3150

EXAMPLE 39

Same as Example 27, except that 1.4 part halocarbon wax (HalocarbonProducts Corp.) is used in place of the Esso wax 3150.

EXAMPLE 40

Same as Example 27, except that 1.0 part silicone S-30 (Union CarbideCo.) is used in place of the Esso wax 3150.

EXAMPLE 41

Same as Example 27, except that 1.0 part silicone L-31 (Union CarbideCo.) is used in place of the Esso wax 3150.

EXAMPLE 42

Same as Example 27, except that 0.5 part Syl-Off 291 (Dow Corning Co.)is used in place of the Esso wax 3150.

EXAMPLE 43

Same as Example 27, except that 1.0 part Syl-Off 291 containing 6%Catalyst 23A (Dow Corning Co.) is used in place of the Esso wax 3150.

EXAMPLE 44

Same as Example 27, except that 1.0 part V-wax (Farbwerke Hoechst AG,poly (octadecyl viny ether) is used in place of the Esso wax 3150.

EXAMPLE 45

Same as Example 27, except that 1.4 parts W-wax (Farbwerke Hoechst AG,hydrogenated animal fat) is used in place of the Esso wax 3150.

EXAMPLE 46

22.6 parts unsaturated polyurethane prepared from 1 mole polyethertriol, 3 moles 2,4-toluene diisocyanate, and 3 moles 2-hydroxyethylacrylate, 20.4 parts 2-hydroxyethyl acrylate, 20.15 partspentaerythritol tetraacrylate, 18.38 parts 1,6-hexanediol diacrylate,12.44 parts trimethylolpropane triacrylate, 6.03 parts acrylatedepoxidized soybean oil (Union Carbide Co., Actomer X-70), 6.0 partsbenzoin isobuty ether, 2.0 parts Esso wax 3150 (paraffin wax, meltingpoint approx. 132° C.) and 30 parts methylene chloride are mixed welluntil a homogeneous solution is obtained.

A carrier paper made of smooth clay coated sheet weighing about 16pounds per ream (500 sheets, 10 inches×25 inches) is coated with theabove solution (using a #20 Mayer rod). The coated paper then is exposedfor 1/10 second to the UV-radiation given off by a medium pressuremercury vapor lamp (Hanovia, 200 2/inch) at a distance of 5 inches fromthe lamp. The distance coincides with the second focal point created bythe elliptical reflector. By this exposure, the coating is cured to ahard, glossy film which has a pencil hardness of 3H.

The radiation cured release coating is then print coated with a clearlacquer composed of 6 parts cellulose acetatebutyrate (Eastman EAB171-40), 55 parts ethylacetate, 28 parts toluene and 11 parts 95%ethanol (printing grade). Print coating is accomplished using a regularvarnish etch cylinder having a depth of about 20 to 40 microns, 120 linescreen and a 15-20 wall (equivalent to #8 Mayer rod). The appliedlacquer coating is dried at 140° F. for 1 minute.

The design printing is then printed over the clear lacquer layer usingpolyamide--nitrocellulose modified ink containing pigment or dye of thecolor desired (ZYROTO WHITE, sold by Gotham Ink and Color Co., whichcontains a titanium dioxide pigment). The area of the design print issmaller than that of the printed lacquer layer and falls wholly withinthe margin of the lacquer layer.

Over the ink, as an overprint, there is then coated a clear adhesivelayer comprising a solution of a heat-activatable thermoplasticpolyamide resin in lacquer form (VERSAMIDE 940, sold by General Mills)followed by drying the adhesive to a dry non-tacky state. The area ofthe adhesive overprint is smaller than that of the lacquer and it fallswholly within the margins of the lacquer layer.

There is no pick-up during the three printing operations.

The heat transfer label, as formed above, is then put in contact with apolyethylene bottle, the surface of which has been treated to render itmore print receptive in a conventional manner such as by flame contact.Heat and pressure are applied to the temporary backing to effectpressing of the adhesive layer against the polyethylene surfaces. Asheat is applied, approximately 350° F., there is no softening of therelease layer or the cellulose acetate layer, but the adhesive overprintis heat-activated to a highly tacky state and bonds to the polyethylenesurface of the bottle. The temporary backing may then be stripped fromthe transfer label or may be left on the transfer and stripped at asubsequent time without danger of delaminating the transfer from thepolyethylene surface. No portion of the release layer is left over thetransfer after stripping of the temporary backing and no portion of thelacquer is removed from the release layer. After cooling and peeling ofthe temporary backing, the bottle so coated is flame treated and theadherence of the lable thereto is determined. Adherence was excellent.

EXAMPLE 47

Same as Example 46, except that 3.0 parts of cyclododecane are used inplace of the Esso wax 3150.

EXAMPLE 48

Same as Example 46, except that 2.0 parts stearic acid are used in placeof Esso wax 3150.

EXAMPLE 49

Same as Example 46, except that 2.4 parts methacryl oxypropyl trimethoxysilane (Union Carbide silane A-174) are used in place of the Esso wax3150.

EXAMPLE 50

Same as Example 46, except that 3.0 parts E-wax (Farbwerke Hoechst AG,Montan type wax) are used in place of the Esso wax 3150.

EXAMPLE 51

Same as Example 46, except that 2.0 parts FL-wsx (Farbwerke Hoechst AG,Montan type wax) are used in place of the Esso wax 3150.

EXAMPLE 52

Same as Example 46, except that 2.4 parts F-wax (Farbwerke Hoechst AG,Montan type wax) are used in place of the Esso wax 3150.

EXAMPLE 53

Same as Example 46, except that 3.0 parts octadecanol are used in placeof the Esso wax 3150.

EXAMPLE 54

Same as Example 46, except that 4.0 parts oleamide (Amour IndustrialChemical Co., Armid O) are used in place of the Esso Wax 3150.

EXAMPLE 55

Same as Example 46, except that 3.0 parts stearyl acrylate are used inplace of the Esso wax 3150.

EXAMPLE 56

Same as Example 46, except that 2.5 parts isodecyl acrylate are used inplace of the Esso wax 3150.

EXAMPLE 57

Same as Example 46, except that 3.0 parts fluorolube LG-160 (HookerChemicals Co.) are used in place of the Esso wax 3150.

EXAMPLE 58

Same as Example 46, except that 3.0 parts halocarbon wax (HalocarbonProducts Corp.) are used in place of the Esso wax 3150.

EXAMPLE 59

Same as Example 46, except that 4.0 parts silicone S-30 (Union CarbideCo.) are used in place of the Esso wax 3150.

EXAMPLE 60

Same as Example 46, except that 4.0 parts silicone L-31 (Union CarbideCo.) are used in place of the Esso wax 3150.

EXAMPLE 61

Same as Example 46, except that 2.0 parts Syl-Off 291 (Dow Corning Co.)are used in place of the Esso wax 3150.

EXAMPLE 62

Same as Example 46, except that 4.0 parts Syl-Off 291 containing 6%Catalyst 23A (Dow Corning Co.) are used in place of the Esso wax 3150.

EXAMPLE 63

Same as Example 46, except that 3.0 parts V-wax (Farbwerke Hoechst AG,poly (octadecyl vinyl ether)) are used in place of the Esso wax 3150.

EXAMPLE 64

Same as Example 46 except that 2.4 parts W-wax (Farbwerke Hoechst AG,hydrogenated animal fat) are used in place of the Esso wax 3150.

EXAMPLE 65

66.3 parts unsaturated polyurethane, prepared from 1 mole polyethertriol (Voranol CP700), 3 moles 2,4-toluene diisocyanate, and 3 moles2-hydroxyethyl acrylate, 72.3 parts trimethylolpropane triacrylate, 1.5parts 2-hydroxyethyl acrylate, 68 parts 1,4-butanediol diacrylate, 50parts acrylated epoxidized soybean oil (Union Carbide Co., ActomerX-70), 2 parts stearyl acrylate, 15.6 parts benzoin isobutyl ether and5.0 parts Union Carbide Co. silicone rubber W-982 (polydimethyl siloxanewith some unsaturation) are mixed well on a roller mill. A clear,colorless homogeneous light oil is obtained as the product.

Films of 0.2-1 mil thickness are applied with wire wound coating rodsonto paper. The coated paper is exposed to the UV-radiation given off bya medium pressure mercury vapor lamp (Hanovia, 200 W/inch) at a distanceof 5 inches from the lamp (second focal point created by the ellipticalreflector). After this exposure the films are cured to hard, glossycoatings.

9 lbs./ream removable adhesive is cast on a paper substrate; then thecoated paper is laminated to the release paper. The force to peel a 1inch wide strip at 12 inches/min. is 43 g./linear inch.

EXAMPLE 66

66.3 parts unsaturated polyurethane, prepared from 1 mole polyethertriol (Voranol CP700), 3 moles 2,4-toluene diisocyanate and 3 moles2-hydroxyethyl acrylate, 72.3 parts trimethylolpropane triacrylate, 15.parts 2-hydroxyethyl acrylate, 68 parts 1,4-butanediol diacrylate, 50parts acrylated epxoidized soybean oil (Union Carbide Co., ActomerX-70), 2 parts stearyl acrylate, 15.6 parts benzoin isobutyl ether and10.0 parts Viscasil 60000 (General Electric; poly (dimethylsiloxane)viscosity 60'000 ctsk) are mixed well on a roller mill. A clearcolorless homogeneous light oil is obtained as the product.

Films of 0.2-1 mil thickness are applied with wire wound coating rodsonto paper. The coated paper is exposed to the UV-radiation given off bya medium pressure mercury vapor lamp (Hanovia, 200 W/inch) at a distanceof 5 inches from the lamp (second focal point created by the ellipticalreflector). After this exposure the films are cured to hard, glossycoatings.

9 lbs./ream removable adhesive is cast on a paper substrate; then thecoated paper is laminated to the release paper. The force to peel a 1inch wide strip at 12 inches/min. is 55 g./linear inch.

EXAMPLE 67

66.3 parts unsaturated polyurethane, prepared from 1 mole polyethertriol (Voranol CP700), 3 moles 2,4-toluene diisocyanate, and 3 moles2-hydroxyethyl acrylate, 72.3 parts trimethylolpropane triacrylate, 1.5parts 2-hydroxyethyl acrylate, 68 parts 1,4-butanediol diacrylate, 50parts acrylated epoxidized soybean oil (Union Carbide Co., ActomerX-70), 2 parts stearyl acrylate, 15.6 parts benzoin isobutyl ether and6.43 parts silicone L-31 (Union Carbide Co.; poly (methyl hydrogensiloxane) are mixed well on a roller mill. A clear, colorless light oilis obtained as the product.

Films of 0.2-1 mil thickness are applied with wire wound coating rodsonto paper. The coated paper is exposed to the UV-radiation given off bya medium pressure mercury vapor lamp (Hanovia, 200 W/inch) at a distanceof 5 inches from the lamp (second focal point created by the ellipticalreflector). After this exposure the films are cured to hard, glossycoatings.

9 lbs./ream removable adhesive is cast on a paper substrate; then thecoated paper is laminated to the release paper. The force to peel a 1inch wide strip at 12 inches/min. is 80 g./linear inch.

EXAMPLE 68

66.3 parts unsaturated polyurethane, prepared from 1 mole polyethertriol (Voranol CP700), 3 moles 2,4-toluene diisocyanate, and 3 moles2-hydroxyethyl acrylate, 72.3 parts trimethylolpropane triacrylate, 1.5parts 2-hydroxyethyl acrylate, 68 parts 1,4-butanediol diacrylate, 50parts acrylated epoxidized soybean oil (Union Carbide Co., ActomerX-70), 2 parts stearyl acrylate, 15.6 parts benzoin isobutyl ether and2.65 parts silicone L-522 (Union Carbide Co., poly dimethyl siloxanewith some hydroxyethyl groups) are mixed well on a roller mill. A clear,homogeneous light oil is obtained as the product.

Films of 0.2-1 mil thickness are applied with wire wound coating rodsonto paper. The coated paper is exposed to the UV-radiation given off bya medium pressure mercury vapor lamp (Hanovia, 200 W/inch) at a distanceof 5 inches from the lamp (second focal point created by the ellipticalreflector. After this exposure the films are cured to hard, glossycoatings.

9 lbs./ream removable adhesive is cast on a paper substrate; then thecoated paper is laminated to the release paper. The force to peel a 1inch wide strip at 12 inches/min. is 30 g./linear inch.

The release coatings of this invention can also be made by radiationcuring of a wax-containing acrylic prepolymer. This is illustrated bythe next example.

EXAMPLE 69

75 parts trimethlolpropane triacrylate, 25 parts neopentyl glycoldiacrylate, 5 parts halocarbon wax (Halocarbon Products Corp., blend ofcompletely halogenated chlorofluorocarbons) and 10 parts benzoinisobutyl ether are milled on a 3 roller mill until homogeneous. A clearsolution is obtained.

Films of 0.2-1 mil thickness are applied with a wire wound coating rodonto paper. The coated paper is exposed to the UV-radiation given off bya medium pressure mercury vapor lamp (Hanovia, 200 W/inch) at a distanceof 5 inches from the lamp (second focal point created by the ellipticalreflector). After this exposure the films are cured to hard, glossycoatings.

9 lbs./ream removable adhesive is cast on a paper substrate; then thecoated paper is laminated to the release paper The force to peel a 1inch wide strip at 12 inches/min is 31 gr./linear inch.

Example 69 illustrates that the new class of radiation curable releasetype coatings according to the invention may be made without anypolyurethane or polyamide component in the unsaturated resin. Apolyurethane or polyamide content in the radiation curable unsaturatedprepolymer is, however, a practical necessity for a satisfactory ink,overprint varnish or panel or tile coating.

Examples 70 and 71 illustrate further polyurethane prepolymers.

EXAMPLE 70

864 parts of a tetra isocyanate (Desmodur HL TDI isocyanurate; preparedfrom 4 moles of 2,4-toluene diisocyanate and 1 mole hexamethylenediisocyanate; MW 864; isocyanate equivalent 216), 1000 parts driedtetrahydrofuran, and 1.0 part stannous octoate are placed in a vesselequipped with an agitator and blanketed with nitrogen. Then 1628 partspoly (propylene oxide) diol (Dow Voranol P400; hydroxyl No. 275; 0.02%H₂ O) are added at such a rate that the temperature of the reactionmixture does not rise above 50° C. The reaction mixture is stirred atthis temperature for an additional one hour. Following this step, 510parts 2-hydroxyethyl acrylate (10% excess) are added at such a rate thatthe reaction mixture starts to reflux gently. The stirring is continuedat reflux for an additional one hour. At the end of this period 2.0parts p-methoxyphenol is added and the solvent is removed under reducedpressure. A clear, colorless, viscous oil is obtained as the product.

EXAMPLE 71

348 parts 2.4-toluene diisocyanate, 500 parts dried tetrahydrofuran and0.5 part stannous octoate are placed in a vessel equipped with anagitator and blanketed with nitrogen. Then 400 parts poly (ethyleneoxide) diol (hydroxyl No. 280) dissolved in 200 parts driedtetrahydrofuran are added at such a rate that the temperature of thereaction mixture does not rise above 50° C. The reaction mixture isstirred at this temperature for an additional one hour. Following thisstep, 286 parts hydroxethyl methacrylate (10% excess) are added at sucha rate that the reaction mixture begins to reflux. Then the stirring iscontinued at reflux for an additional one hour. At the end of thisperiod 1.0 part p-methoxy phenol is added and the solvent is removedunder reduced pressure. A clear, colorless, viscous oil is obtained asthe product.

EXAMPLE 72

20.27 parts unsaturated polyurethane prepared from 1 mol polyethertriol, 3 moles 2,4-toluene diisocyanate, and 3 moles 2-hydroxyethylacrylate, 11.16 parts trimethylolpropane triacrylate, 7.39 partsneopentylglycol diacrylate, 6.16 parts 1,6-hexanediol diacrylate, 17.45parts 2-hydroxyethyl acrylate, 5.34 parts acrylated epoxidized soybeanoil (Union Carbide Co., Actomer X-70), 7.39 parts benzoin isobutylether, 4.72 parts silicone oil (Dow Corning, PA-11), and 2.67 partsfluorochlorocarbon oil (Halocarbon Products Corp., Halocarbon oil0.8/100) are mixed well until a homogeneous solution is obtained.

A carrier paper made of a smooth clay coated sheet weighing 16 poundsper ream is coated with the above solution. The coated paper is thenexposed for 1/10 second to the UV-radiation given off by a mediumpressure mercury vapor lamp (Hanovia 200 W/inch) at a distance of fiveinches from the lamp. This exposure cures the coating to a hard, glossyfilm.

The radiation cured release coating is then processed further as setforth in Example 46.

Other waxy materials which can be used in formulations similar toExample 72 in substitution for the silicone oil and fluorocarbon oil ofthat Example are given in Examples 73-85 below.

EXAMPLE 73

4.72 parts silicone oil (Dow Corning, PA-11)

2.67 parts Fluorochlorocarbon oil (Halocarbon Products Corp., Halocarbonoil 437)

EXAMPLE 74

1.4 parts ester wax (Hoechst, E-Wax)

1.4 parts Fluorochlorocarbon oil (Halocarbon Products Corp., Halocarbonoil 0.8/100)

EXAMPLE 75

1.4 parts cyclododecane, dissolved in 4.2 parts methylene chloride (MC)

1.4 parts Halocarbon oil 0.8/100

EXAMPLE 76

1.4 parts cyclododecane dissolved in 4 parts MC

1.4 parts Halocarbon oil 437

EXAMPLE 77

0.94 parts cyclododecane dissolved in 3 parts MC

4.7 parts dimethyldiphenyl polysiloxane (General Electric Co., SF-1153Silicone)

EXAMPLE 78

0.94 parts cyclododecane, dissolved in 3 parts MC

4.7 parts vinyl triethoxy silane (Union Carbide Corp., Silane A-151)

EXAMPLE 79

0.94 parts cyclododecane, dissolved in 3 parts MC

4.70 parts silicone oil (Union Carbon, Silicoen Y-2902)

EXAMPLE 80

0.94 parts cyclododecane, dissolved in 3 parts MC

4.70 parts non-ionic organosilicone fluid (Union Carbide, Silicone L-49)

EXAMPLE 81

0.94 parts cyclododecane, dissolved in 3 parts MC

4.70 parts non-ionic organosilicone fluid (Union Carbide, SiliconeL-7001)

EXAMPLE 82

0.94 parts cyclododecane, dissolved in 3 parts MC

4.70 parts N-beta (aminoethyl)-gamma aminopropyltrimethoxy silane (UnionCarbide, Silane A-1120)

EXAMPLE 83

0.94 parts cyclododecane, dissolved in 3 parts MC

4.70 parts non-ionic organosilane fluid (Union Carbide, Silicone L-522)

EXAMPLE 84

2.29 parts fluorochlorocarbon wax (Halocarbon Products Corp., Halocarbonwax 6.000), dissolved in 9.3 parts tetrahydrofurane

EXAMPLE 85

0.93 parts dimethyl polysiloxane oil (Union Carbide, Silicone L-522)

2.78 parts fluorochlorocarbon oil (Halocarbon Products Corp., Halocarbonoil 437)

Examples 86, 87, 91, 92 and 93 illustrate radiation curable releasecoating prepared from acrylated epoxy resins dispersed in acrylatemonomers. Examples 88, 89 and 90 illustrate release coatings preparedfrom unsaturated polyester resins dispersed in acrylate monomers.Example 95 is a release coating formulation of acrylate monomers withoutprepolymer. Examples 96 and 97 illustrate release coatings prepared fromepoxide resins polymerizable by release of catalyst on exposure toionizing radiation. Examples 98, 99 and 100 depict release coatingsbased on a radiation curable polyene-polythiol system. Examples 101, 102and 103 illustrate release coatings prepared from polyunsaturatedurethanes in acrylate esters, while Example 104 illustrates anotherrelease coating prepared from acrylic esters.

EXAMPLE 86

33.06 parts Epoxryl 25-A-60 (Shell Chem. Co., 60% dimethacrylate esterof bis glycidyl ether of Bisphenol A in acetone solvent), 33.06 partstrimethylolpropane triacrylate, 14 parts pentaerythritol tetraacrylate,14 parts neopentylglycol diacrylate, 33.46 parts 1,6-hexanedioldiacrylate, 14 parts 2-hydroxyethyl acrylate, 8.26 parts acrylatedepoxidized soybean oil (Union Carbide Co., Actomer X-70), 9.91 partsbenzoin isobutyl ether, and 2.64 parts gamma-methacryloxypropyltrimethoxysilane (Union Carbide Co., Silane A-174) are mixed welluntil a homogeneous solution is obtained.

The resulting solution is then processed further as set forth in Example72.

EXAMPLE 87

20.00 parts Epocryl DRH-303 (Shell Chem. Co., diacrylate ester of liquidbisphenol A resin), 20.00 parts trimethylolpropane triacrylate, 13.00parts pentaerythritol tetraacrylate, 15.21 parts neopentylglycoldiacrylate, 18.25 parts 1,6-hexanediol diacrylate, 14 parts2-hydroxyethyl acrylate, 8.50 parts acrylated epoxidized soybean oil(Union Carbide Co., Actomer X-70), 10.20 parts benzoin isobutyl ether,1.10 part cyclododecane, dissolved in 3.5 parts methylene chloride, and5.00 parts N-beta-aminoethyl-gamma-aminopropyltrimethoxysilane (UnionCarbide Co., Silane A-1120) are mixed well until a homogeneous solutionis obtained.

The resulting solution is then processed further as set forth in Example72.

EXAMPLE 88

20.10 parts unsaturated polyester, made from adipic acid, maleicanhydride, and hexanediol; molecular weight approx. 3000, 4 double bondsper polyester; 20.00 parts trimethylolpropane triacrylate, 20 partspentacrythritol tetraacrylate, 20.00 parts neopentylglycol diacrylate,20.00 parts 1,6-hexanediol diacrylate, 5.10 parts 2-hydroxyethylacrylate, 5.50 parts acrylated epoxidized soybean oil (Union CarbideCo., Actomer X-70) 10.00 parts benzoin isobutyl ether, 1.50 partscyclododecane, dissolved in 4.5 parts methylene chloride, and 1.50 partsfluorochlorocarbon oil (Halocarbon Products Corp., Halocarbon oil 437)are mixed well until a homogeneous solution is obtained.

The resulting solution is then processed further as set forth in Example72.

EXAMPLE 89

20.00 parts unsaturated polyester, made from adipic acid, maleicanhydride, and hexanediol; molecular weight approx. 3000; 4 double bondsper polyester; 20.00 parts trimethylolpropane triacrylate, 15 partspentaerythritol tetraacrylate, 20.00 parts neopentylglycol diacrylate,20.00 parts 1,6-hexanediol diacrylate, 6.00 parts 2-hydroxyethylacrylate, 5.00 parts acrylated epoxidized soybean oil (Union CarbideCo., Actomer X-70), 9.00 parts benzoin isobutyl ether, 1.20 partscyclododecane, dissolved in 3.6 parts methylene chloride, and 5.00 partsN-beta-animoethylgamma-aminopropyltrimethoxysilane (Union Carbide, Co.,Silane A-1120) are mixed well until a homogeneous solution is obtained.

The resulting solution is then processed further as set forth in Example72.

EXAMPLE 90

20.00 parts unsaturated polyester, made from adipic acid, maleicanhydride, and hexanediol; molecular weight approx. 3000; 4 double bondsper polyester, 20.00 parts trimethylolpropane triacrylate, 20 partspentaerythritol tetraacrylate, 20.00 parts neopentylglycol diacrylate,20.00 parts 1,6-hexanediol diacrylate, 5.00 parts 2-hydroxyethylacrylate, 7.00 parts acrylated epoxidized soybean oil (Union CarbideCo., Actomer X-70), 10.00 parts benzoin isobutyl ether, 1.20 partscyclododecane, dissolved in 3.6 parts methylene chloride, and 5.00 partsdimethyl diphenyl polysiloxane (General Electric Co., Silicone SF-1153)are mixed well until a homogeneous solution is obtained.

The resulting solution is then processed further as set forth in Example72.

EXAMPLE 91

20.00 parts Epocryl DRH-303 (Shell Chem. Co., diacrylate ester of liquidbisphenol A resin), 20.00 parts trimethylolpropane triacrylate, 12.00parts pentaerythritol tetraacrylate, 20.00 parts neopentylglycoldiacrylate, 15.00 parts 1,6-hexanediol diacrylate, 5.00 parts2-hydroxyethyl acrylate, 6.00 parts acrylated epoxidized soybean oil(Union Carbide Co., Actomer X-70), 10.00 parts benzoin isobutyl ether,1.50 parts cyclododecane dissolved in 4.5 parts methylene chloride, and1.50 parts fluorochlorocarbon oil (halocarbon Products Corp., Halocarbonoil 437) are mixed well until a homogeneous solution is obtained.

The resulting solution is then processed further as set forth in Example72.

EXAMPLE 92

20.00 parts Epocryl DRH-303 (Shell Chem. Co., diacrylate ester of liquidbisphenol A resin), 20.00 parts trimethylolpropane triacrylate, 12.00parts pentaerythritol tetraacrylate, 20.00 parts neopentylglycoldiacrylate, 15.00 parts 1,6-hexanediol diacrylate, 5.00 parts2-hydroxyethyl acrylate, 6.00 parts acrylated epoxidized soybean oil(Union Carbide Co., Actomer X-70), 10.00 parts benzoin isobutyl ether,1.20 parts cyclododecane, dissolved in 3.6 parts methylene chloride,5.00 parts dimethyl diphenyl polysiloxane (General Electric Co.,Silicone SR-1153) are mixed well until a homogeneous solution isobtained.

The resulting solution is then processed further as set forth in Example72.

EXAMPLE 93

20.00 parts Epocryl DRH-303 (Shell Chem. Co., diacrylate ester of liquidbisphenol A resin), 20.00 parts trimethylolpropane triacrylate, 12.00parts pentaerythritol tetraacrylate, 20.00 parts neopentylglycoldiacrylate, 15.00 parts 1,6-hexanediol diacrylate, 5.00 parts2-hydroxyethyl acrylate, 6.00 parts acrylated epodidized soybean oil(Union Carbide Co., Actomer X-70), 10.00 parts benzoin isobutyl ether,and 2.00 parts cyclododecane, dissolved in 6.0 parts methylene chlorideare mixed well until a homogeneous solution is obtained.

The resulting solution is then processed further as set forth in Example72.

EXAMPLE 95

Ingredients

20.0 parts polypropylene glycol TP 340 triacrylate

15.0 parts trimethylolpropane triacrylate

15.0 parts pentaerythritol tetraacrylate

15.0 parts neopentylglycol diacrylate

15.0 parts 1,6-hexanediol diacrylate

10.0 parts 2-hydroxyethyl acrylate

5.0 parts acrylated epoxidized soybean oil (Union Carbide Co., ActomerX-70)

10.0 parts benzoin isobutyl ether

1.0 part cyclododecane, dissolved in 3.0 parts methylene chloride

4.0 parts dimethyl diphenyl polysiloxane (General Electric SiliconeSF-1153).

EXAMPLE 96

Ingredients

212.0 parts Diglycidyl ether of bisphenol A

106.0 parts (3,4-epoxycyclohexyl)-methyl 3,4-epoxycyclohexanecarboxylate.

3.18 parts Alkyl glycidyl ether in which alkyl groups are predominantlydodecyl and tetradecyl

4.0 parts propylene carbonate, containing dissolved 2.45 parts ofp-chlorobenzene diazonium hexafluorophosphate as the catalyst precursor

0.75 part N,N-dimethyl acetamide as gelation inhibitor

3.0 parts cyclododecane dissolved in 9.0 parts methylene chloride

12.0 parts nonionic organosilicone fluid (Union Carbide L-522 Silicone).

EXAMPLE 97

Ingredients

212.0 parts Diglycidyl ether of bisphenol A

106.0 parts (3,4-epoxycyclohexyl)-methyl 3,4-epoxyclohexane carboxylate

3.18 parts alkyl glycidyl ether in which alkyl groups are predominantlydodecyl and tetra decyl

4.0 parts propylene carbonate, containing dissolved 2.45 parts ofp-chlorobenzene diazonium hexafluorophosphate as the catalyst precursor

0.75 part N,N-dimethyl acetamide as gelation inhibitor

3.0 parts Halocarbon wax 6.00 (Halocarbon Products Corp.).

EXAMPLE 98

Ingredients

534.0 parts bis (diallylamine) adduct of bis glycidyl ether of bisphenolA

488.0 parts pentaerythritol tetra-beta-mercaptopropionate

1.0 part dibenzosuberone

30.0 parts Halocarbon oil 437 (Halocarbon Produccts Corp.).

EXAMPLE 99

Ingredients

534.0 parts bis (diallyl amine) adduct of bisglycidyl ether of bisphenolA

488.0 parts pentaerythritol tetra-beta-mecaptopropionate

1.0 part dibenzosuberone

10.0 parts cyclododecane, dissolved in 30 parts methylene chloride

50.0 parts N-beta-aminoethyl-gamma-aminopropyltrimethoxy silane (UnionCarbide Co., Silane A-1120).

EXAMPLE 100

Ingredients

584.0 parts bis(diallylamine) adduct of Epon 828 (Shell Chemical Co.;bis glycidyl ether of bisphenol A type resin with epoxy equivalent ofapprox. 195)

488.0 parts pentaerythritol tetra-beta-mercaptopropionate

1.5 parts dibenzosuberone

10.0 parts cyclododecane, dissolved in 30 parts methylene chloride

50.0 parts dimethyl diphenyl polysiloxane (General Electric Co.,Silicone SF-1153).

EXAMPLE 101

Ingredients

20.0 parts diunsaturated polyetherurethane [made from 324 parts poly(tetra-methylene ether) glycol (Quaker Oats Co.; OH -No. 37.1 348 partstoluene diisocyanate, and 232 parts 2-hydroxy ethyl acrylate]

15.0 parts pentaerythritol tetra acrylate

15.0 parts trimethylol propane triacrylate

15.0 parts 1,6-Hexane diol diacrylate

15.0 parts neopentylglycoldiacrylate

10.0 parts 2-hydroxyethyl acrylate

10.0 parts benzoin isobutyl ether

1.0 part cyclododecane, dissolved in 3.0 parts methylene chloride

2.0 parts Halocarbon oil 437 (Halocarbon Products Corp.)

EXAMPLE 102

Ingredients

20.0 parts diunsaturated polyurethane [made from 458 parts adipreneL-100 (duPont) diisocyanate and 53.4 parts 2-hydroxyethyl acrylate]

15.0 parts pentaerythritol tetracrylate

15.0 parts trimethylol propane triacrylate

15.0 parts 1,6-hexanedioldiacrylate

15.0 parts neopentylglycol diacrylate

10.0 parts 2-hydroxyethylacrylate

10.0 parts benzoin isobutyl ether

1.0 part cyclododecane, dissolved in 3.0 parts methylene chloride

3.0 parts gamma-methacryl oxypropyltrimethoxy silane (Union Carbide Co.,Silane A-174).

EXAMPLE 103

Ingredients

20.0 parts diunsaturated polyester-urethane [made from 323 partspolyesterdiol (RC polyester S 101-35 by Hooker Chemical Co.; MW 3232),34.8 parts toluenediisocyanate, and 23.2 parts 2-hydroxyethyl acrylate)

15.0 parts pentaerythritol tetra acrylate

15.0 parts trimethylol propane triacrylate

15.0 parts 1,6-hexane diol diacrylate

15.0 parts neopentyl glycol diacrylate

10.0 parts 2-hydroxyethyl acrylate

10.0 parts benzoin isobuty ether

1.0 part cyclododecane, dissolved in 3.0 parts methylene chloride

4.0 parts nonionic organosilicone fluid (Union Carbide Co., SiliconeL-522).

EXAMPLE 104

30.0 parts acrylic ester (made from 1 mole glycerol, 2 moles glacialacrylic acid, 0.5 mole maleic anhydride, and 0.02 mole p-toluenesulfonic acid)

30.0 parts trimethylol propane triacrylate

15.0 parts pentaerythritol tetraacrylate

15.0 parts neopentylglycol diacrylate

15.0 parts 1,6-hexanediol diacrylate

10.0 parts 2-hydroxyethyl acrylate

5.0 parts acrylated epoxidized soybean oil (Union Carbide Co., ActomerX-70)

10.0 parts benzoin isobutyl ether

1.0 part cyclododecane, dissolved in 3.0 parts methylene chloride

3.0 parts N-beta-aminoethyl-gamma-aminopropyltrim ethoxy silane (UnionCarbide Co., Silane A-1120).

Examples 105-114 illustrate coatings and films which are radiationcurable and which have good film strength, good adhesion, good abrasionand solvent resistance, and which can also be cast to reproduce withgood fidelity the surface over which they are cast. They incorporate, inthe radiation curable films as herein disclosed, other essentiallylinear polymers of generally higher molecular weight which are solublein the radiation-curable liquid composition. They should have amolecular weight of at least about 2,000 up to the limit of solubility,and preferably about 10,000 to 20,000. These polymers add bulk,strength, and control shrinkage in the cured composite films. The addedpolymers are pre-polymerized and generally do not react during radiationcuring, although they can advantageously include reactive groups, suchas ethylenic unsaturation, for example, as end groups, which willco-polymerize during curing. By inclusion of a wax or wax-like materialof limited compatibility as herein disclosed, and which migrate to thesurface, an oxygen barrier is provided which permits the films to becured in the presence of oxygen, e.g., in air, and which provide filmswith release properties.

EXAMPLE 105

The following ingredients are mixed well, all parts being by weight.

11.4 parts unsaturated polyether-polyurethane prepolymer, prepared from1 mole polyether triol, 3 moles 2,4 toluenediisocyanate, and 3 moles2-hydroxyethyl acrylate, according to Example 1 above

17.35 parts trimethylol propane triacrylate

10.65 parts neopentyl glycol diacrylate

2.4 parts acrylated epoxidized soybean oil (ACTOMER X-70, Union CarbideCorp.)

3.95 parts 2-hydroxyethyl acrylate

0.45 parts cyclododecane, dissolved in 2.3 parts methylene chloride

50.0 parts methyl methacrylate copolymer, 40% solids in a mixture oftoluene and isopropanol (ELVACITE 6014, DuPont).

After mixing well, the solvents are removed at room temperature in thedark, under reduced pressure, and in the presence of copper shaving aspolymerization inhibitor. Thereafter, the following ingredients areadded.

6.0 parts benzoin isobutyl ether (photoinitiator)

2.15 parts N-beta (aminoethyl)-gamma-aminopropyl trimethoxy silane(Silane A-1120, Union Carbide Corp.), (a limited-compatibilitymaterial).

The resulting liquid composition can be coated as hereinbeforedescribed. It can also be cast, e.g. over an optical reflective patternon a steel surface, with or without release agent, rapidly cured withradiation and stripped to provide a self-supporting film containing onone surface a good replica of the optical pattern.

EXAMPLES 106-114

Examples 106-114 below illustrate other additional polymers which can besubstituted for ELVACITE 6104 in Example 105 to provide, by the sameprocedure, good radiation curable casting films and release films orcoatings.

                  TABLE I                                                         ______________________________________                                        Example                                                                       No.     Parts   Ingredients                                                   ______________________________________                                        106     17.0    G-CURE 869 S, General Mills Chemical                                          Inc., a hydroxy functional acrylic                                            copolymer, 60% solids in a mixture                                            of xylene and cellosolve acetate.                             107     10.0    PM Polymer (Phillips Petroleum Co.,                                           a mercaptan terminated hydrocarbon                                            polymer).                                                     108     42.0    Bakelite T-24-g (Union Carbide Corp.,                                         a vinyl alcohol-vinyl acetate co-                                             polymer, 25% solids in toluene).                              109     40.0    Bakelite Vinyl Butyral XYLS-4 (Union                                          Carbide Corp., 25% solids).                                   110     10.0    Polyketone Resin 250 (Union Carbide                                           Corp., dissolved in 50 parts toluene).                        111     17.0    Spencer-Kellogg DV-2230, an aliphatic                                         polyurethane lacquer, 30% solids in                                           mixture of tetrahydrofuran and iso-                                           propanol.                                                     112     10.0    Castomer P-0010 (Witco Chemical Co.,                                          an unsaturated polyurethane dissolved                                         in 50 parts methylene chloride).                              113     20.0    Acryloid AT-71 (Rohm & Haas Co., a                                            polyacrylate with carboxyl function-                                          ality, 50% solids).                                           114     20.0    Acryloid AT-63 (Rohm & Haas Co.,                                              a polyacrylate with hydroxyl                                                  functionality, 50% solids in xylene).                         ______________________________________                                    

In the reactive polyamide prepolymers herein described, the polyamideshould have primary amine end groups and at least one secondary amine inthe polymer chain. They are prepared, for example, from essentiallysaturated dibasic acids such as dimerized fatty acids and triamines suchas diethylene triamine, excess amine being employed to provide amine endgroups. Each reactive polyamide resin molecule is, according to thisinvention, reacted with at least three molecules of an unsaturateddibasic acid, reaction being terminated when the acid molecule hasformed one amide linkage and before significant cross-linking occurs.The useful unsaturated dibasic acids are maleic, fumaric, itaconic and5-norbornene-2,3 dicarboxylic acids, or their lower alkyl ester oranhydrides thereof. The unsaturated groups of these acids co-polymerizewith radiation polymerizable vinyl monomers to provide radiation curedfilms, but do not react with the amine groups of the reactive polyaminewhen condensed therewith. These prepolymers are especially useful asinks and can be diluted with vinyl monomers including acrylates,styrene, vinyl ethers, vinyl acetate, and the like which can beradiation co-polymerized therewith.

EXAMPLE 115 Coating with Oxygen-barrier Properties

39.5 parts reaction product from Example 3, 23.3 partstrimethylolpropane triacrylate, 23.3 parts neopentyl glycol diacrylate,8.7 parts 2-hydroxyethyl acrylate, and 28.0 parts of a 25% solution ofvinylidene chloride-acrylonitrile copolymer (Saran F-310, Dow ChemicalCompany) in methylethyl ketone are mixed well. Then the methyl ethylketone solvent is removed at room temperature under reduced pressure. Tothe solvent free residue is added 8.0 parts benzoin isobutyl ether. Thecomposition is mixed on a roller mill and a colorless medium oil isobtained. Films are applied and cured as shown in Example 10. The curedfilms have more than twice the oxygen-barrier properties compared withan identical film without the Saran F-310.

EXAMPLE 116 Coating with Oxygen-barrier Properties

39.5 parts reaction product from Example 3, 23.3 partstrimethylolpropane triacrylate, 23.3 parts neopentyl glycol diacrylate,8.7 parts 2-hydroxyethyl acrylate, and 4 parts of cyclododecane aremixed on a roller mill until a clear, colorless light oil is obtained.Then 8 parts of benzoin isobutyl ether are added and the milling iscontinued for a short while. Films are applied and cured as shown inExample 10. The cured films have more than twice the oxygen barrierproperties compared with an identical film without the cyclododecane.

EXAMPLE 117 Coating with Oxygen-barrier Properties

Ingredients:

212.0 parts Diglycidyl ether of bisphenol A

106.0 parts (3,4-epoxycyclohexyl)-methyl 3,4-epoxycyclohexanecarboxylate

3.18 parts Alkyl glycidyl ether in which alkyl groups are predominantlydodecyl and tetradecyl

4.0 parts propylene carbonate, containing dissolved 2.45 parts ofp-chlorobenzene diazomium hexafluorophosphate as the catalyst precursor

0.75 parts N,N-dimethyl acetamide as gelation inhibitor

13.2 parts cyclododecane dissolved in 13.0 parts methylene chloride

EXAMPLE 118 Coating with Oxygen-barrier properties

Ingredients

212.0 parts Diglycidyl ether of bisphenol A

106.0 parts (3,4-epoxycyclohexyl)-methyl 3,4-epoxycyclohexanecarboxylate.

3.18 parts Alkyl glycidyl ether in which alkyl groups are predominantlydodecyl and tetradecyl

4.0 parts propylene carbonate, containing dissolved 2.45 parts ofp-chlorobenzene diazomium hexafluorophosphate as the catalyst precursor

0.75 parts N,N-dimethyl acetamide as gelation inhibitor

100.0 parts of a 25% solution of vinylidene chloride-acrylonitrilecopolymer (Saran F-310, Dow Chemical Co.) in methylethyl ketone aremixed well. Then the methylethyl ketone is removed at room temperatureunder reduced pressure.

EXAMPLE 119 Coating with Oxygen-barrier properties

Ingredients

534.0 parts bis (diallyl amine) adduct of bisglycidyl ether of bisphenolA

488.0 parts pentaerythritol tetra-beta-mecaptopropionate

1.0 part dibenzosuberone

40.0 parts cyclododecane, dissolved in 40 parts methylene chloride

EXAMPLE 120 Coating with Oxygen-barrier properties

Ingredients

534.0 parts bis (diallyl amine) adduct of bisglycidyl ether of bisphenolA

488.0 parts pentaerythritol tetra-bis-mecaptopropionate

1.0 part dibenzosuberone

280.0 parts of a 25% solution of vinylidene chloride-acrylonitrilecopolymer (Saran F-310; Dow Chemical Co.) in methyl ethyl ketone aremixed well. Then the methyl ethyl ketone is removed at room temperatureunder reduced pressure.

What is claimed is:
 1. A radiation curable, film-forming, spreadable,unsaturated prepolymer material comprisinga reactive amine-containingpolyamide prepolymer modified by condensation with a member selectedfrom the group consisting of an unsaturated dicarboxylic acid anhydrideor lower ester of such an acid, the portion of the modifying member tothe remainder of the polymer being in the range from 10:1 to 1:10; anadmixture, with the modified amine-containing polyamide prepolymer, ofone or more acrylate or methacrylate monomers; and an aromatic ketonephotoinitiator.
 2. A radiation curable prepolymer material as defined inclaim 1 in which:said unsaturated dicarboxylic acid anhydride or esterthereof is a material selected from the group consisting of dimethylitaconate and 5-norbonene-2, 3, dicarboxylic anhydride thereof.
 3. Aradiation curable prepolymer material as defined in claim 1 inwhich:said acrylate or methacrylate monomers are selected from the groupconsisting of trimethylolpropane triacrylate, tetraethylene glycoldiacrylate and acrylic acid, hydroxyethyl acrylate, neopentyl glycoldiacrylate, acrylated epoxidized soybean oil, hexanediol diacrylate, 1,4-butanediol diacrylate, pentaerythritol triacrylate, butyl acrylate,isodecylacrylate, octadecyl acrylate, corresponding methacrylates, andmixtures thereof.
 4. A radiation curable prepolymer material as definedin claim 1 wherein said aromatic ketone photoiniator is selected fromthe group consisting of:benzoin lower alkyl ethers, acetophenone,benzophenone, benzil, Michlers ketone, 2,2-diethoxyacetophenone2,2-dimethoxy-2-phenylacetophenone, "Sandoray-1000" (a homogeneoushalogen containing alkylarylketone), and mixtures thereof.
 5. Aradiation curable, film-forming, spreadable, unsaturated prepolymermaterial as defined in claim 1 in which the amine-containing polyamideprepolymer contains primary and/or secondary amine groups.
 6. Aradiation curable, film-forming, spreadable, unsaturated prepolymermaterial as defined in claim 1 in which said primary and/or secondaryamine groups are positioned internally and/or terminally.
 7. A radiationcurable, film-forming, spreadable, unsaturated prepolymer material asdefined in claim 1 in which hydrocarbon wax, oleamide, polysiloxane,silicone or silane, fluoracarbon oil or wax, or any two or more of them,is added to said one or more acrylic or methacrylic monomers.
 8. Aradiation curable, film-forming, spreadable, unsaturated prepolymermaterial as defined in claim 1 in which the modified polyamide isproduced by heating a methyl or ethyl ester, or mixed methyl and ethylesters, of one or more dicarboxy unsaturated acids, followed byevaporating methanol, ethanol, or both, and excess ethyl or methylesters, or both, and completing the evaporation in the presence of aninhibitor of premature polymerization.
 9. A radiation curable,film-forming, spreadable, unsaturated prepolymer material as defined inclaim 8 in which the inhibitor is p-methoxyphenol.
 10. A radiationcurable, film-forming, spreadable, unsaturated prepolymer material asdefined in claim 8 in which the ester of a dicarboxy unsaturated acid isa substance selected from the group consisting of dimethyl maleate,diethyl maleate, dimethyl fumarate, diethylfumarate, dimethyl itaconate,and mixtures thereof.
 11. A radiation curable, film-forming, spreadable,unsaturated prepolymer material as defined in claim 8 in which themodified prepolymer is obtained by heating 5-norbornene-2, 3 dicarboxylanhydride with a polyamide amine.
 12. A radiation curable, film-forming,spreadable unsaturated prepolymer material as defined in claim 8 inwhich the modified prepolymer is obtained by heating a polyamidepolyamine with an ethyl or methyl ester, or both, of an unsaturateddicarboxylic acid, or 5-norbornene-2, 3, dicarboxylic acid and strippingvolatiles.
 13. A radiation curable, film-forming, spreadable,unsaturated prepolymer material as defined in claim 1 in which a pigmentis added with stearyl acrylate.
 14. A radiation curable, film-forming,spreadable, unsaturated prepolymer material as defined in claim 13 inwhich the pigment is selected from the class consisting of litholrubine, molybdate orange, chrome yellow, phthalocanine blue, carbonblack, or a dye.